Optical fiber and method of making the same

ABSTRACT

An optical fiber is composed of silica glass and comprises a center core region doped with F element, a ring core region doped with GeO 2 , and an inner cladding region doped with F element; wherein a buffer layer composed of undoped SiO 2  or SiO 2  doped with one or both of P and Cl or a concentration gradient region in which GeO 2  concentration radially decreases toward the boundary is provided between the center core region and the ring core region.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to an optical fiber having a ring core portion, and a favorable method of making the same.

[0003] 2. Related Background Art

[0004] Dispersion-shifted optical fibers have a zero-dispersion wavelength, where their chromatic dispersion value becomes zero, in the wavelength range of 1.55 μm. Known as one kind thereof are those of a ring-shaped structure in which a ring core region having a higher refractive index and a cladding region having a lower refractive index are disposed concentrically around a center core region. A dispersion-shifted optical fiber having such a ring-shaped structure of refractive index profile is manufactured by drawing an optical fiber preform having a similar refractive index profile.

[0005] The refractive index profile of this optical fiber preform can be realized by employing silica glass as a main ingredient, adding F (fluorine) element to a center core portion which is to become the center core region of the optical fiber, and adding GeO₂ (germanium dioxide) to a ring core portion which is to become the ring core region. This optical fiber preform is subjected to melt spinning, i.e., so-called drawing, an optical fiber having a desirable refractive index profile may be obtained.

SUMMARY OF THE INVENTION

[0006] However, upon drawing, the optical fiber preform is heated and, at this time, the F element added to the center core portion diffuses into its surrounding regions, whereas Ge added to the ring core portion diffuses into the center core portion and the outer cladding region. Due to this mutual diffusion, transmission loss would increase. Also, when Ge and F mingle with each other, then GeF₄ or GeO may be produced in a heating and unifying process, so as to generate bubbles, which deteriorate the quality of the optical fiber to be made. As a result, there has been a problem that desirable fiber characteristics may not be obtained.

[0007] In order to overcome the above-mentioned problem, it is an object of the present invention to provide an optical fiber of a ring-shaped structure having a region doped with F element and a region doped with Ge, which can be manufactured stably and has a desirable refractive index profile; and a method of making the same.

[0008] For overcoming the above-mentioned problem, the optical fiber in accordance with the present invention is composed of silica glass, having a center core region doped with F element and a ring core region doped with GeO₂, wherein a buffer layer made of undoped SiO₂ (silicon dioxide) or SiO₂ doped with both or one of P (phosphorus) and Cl (chlorine) is disposed between the center core region and the ring core region.

[0009] The optical fiber in accordance with the present invention can be made by drawing an optical fiber preform having a cross-sectional profile similar to that of this optical fiber. Namely, the optical fiber preform also has a buffer layer made of undoped SiO₂ or SiO₂ doped with one or both of P and Cl. When this optical fiber is drawn, the mutual diffusion of F and Ge between the ring core region and the center core region is suppressed due to the existence of buffer layer. The fact that this buffer layer exists in the resulting optical fiber indicates that the mutual dispersion suppressing effect sufficiently functions, so as to maintain fiber characteristics.

[0010] Preferably, the thickness of the buffer layer is at least 0.01 μm but not greater than 5 μm. If the buffer layer is thinner than the lower limit of this range, there is a possibility of the mutual diffusion of Ge and F occurring beyond the buffer layer. On the other hand, if the buffer layer is thicker than the upper limit of the range, the bending loss occurring when the optical fiber is bent may become unfavorably large.

[0011] Alternatively, the optical fiber in accordance with the present invention is composed of silica glass, having a center core region, a ring core region doped with GeO₂ (germanium dioxide), and an inner cladding region doped with F (fluorine) element which are arranged concentrically, wherein a buffer layer made of undoped SiO₂ or SiO₂ doped with both or one of P and Cl is disposed between the ring core region and the inner cladding region.

[0012] The mutual diffusion of F and Ge between the ring core region and the inner cladding region when drawing an optical fiber preform having a similar structure is suppressed due to the existence of buffer layer in this case as well. Similarly, the fact that this buffer layer exists in the resulting optical fiber indicates that the mutual dispersion suppressing effect sufficiently functions, so as to maintain fiber characteristics.

[0013] In this case, the thickness of the buffer layer is preferably 0.01 μm or greater. It is because of the fact that there is a possibility of the mutual diffusion of Ge and F occurring beyond the buffer layer if the buffer layer is thinner than this lower limit. On the other hand, the change in bending loss occurring upon bending the optical fiber depending on the thickness of the buffer layer in this case is smaller than that in the case where the buffer layer is formed between the ring core region and the center core region, whereby the buffer layer can be made thicker.

[0014] Alternatively, the optical fiber in accordance with the present invention is comprised of silica glass, having a center core region doped with F element and a ring core region doped with GeO₂; wherein, letting a [μm] be the radius of the center core region, and C_(G)(r) [wt %] be the concentration of GeO₂ in the ring core region at a position separated from the center by a radius r [μm], the concentration gradient Y_(G1) [wt %·μm²] of GeO₂ in a boundary portion of the ring core region with respect to the center core region defined by: $\begin{matrix} {y_{G1} = {\int_{a}^{a + 1}{\left( {{{rC}_{G}(r)}{\exp \left( {a - r} \right)}} \right){r}}}} & (1) \end{matrix}$

[0015] is set to 100 wt %·μm² or less; or, letting C_(F)(r) [wt %] be the concentration of F element in the center core region at a position separated from the center by a radius r [μm], the concentration gradient y_(F1) [wt %·μm²] of F element in a boundary portion of the center core region with respect to the ring core region defined by: $\begin{matrix} {y_{F1} = {\int_{a - 1}^{a}{\left( {{{rC}_{F}(r)}{\exp \left( {r - a} \right)}} \right){r}}}} & (2) \end{matrix}$

[0016] is set to 18 wt %·μm² or less.

[0017] Alternatively, the optical fiber in accordance with the present invention is composed of silica glass, having a center core region, a ring core region doped with GeO₂, and an inner cladding region doped with F element which are arranged concentrically; wherein, letting b [μm] be the radius of the ring core region, and C_(G)(r) [wt %] be the concentration of GeO₂ in the ring core region at a position separated from the center by a radius r [μm], the concentration gradient Y_(G2) [wt %·μm²] of GeO₂ in a boundary portion of the ring core region with respect to the inner cladding region defined by: $\begin{matrix} {y_{G2} = {\int_{b - 1}^{b}{\left( {{{rC}_{G}(r)}{\exp \left( {r - b} \right)}} \right){r}}}} & (3) \end{matrix}$

[0018] is set to 180 wt %·μm² or less; or, letting C_(F)(r) [wt %] be the concentration of F in the inner cladding region at a position separated from the center by a radius r [μm], the concentration gradient Y_(F2) [wt %·μm²] of F element in a boundary portion of the inner cladding region with respect to the ring core region defined by: $\begin{matrix} {y_{F2} = {\int_{b}^{b + 1}{\left( {{{rC}_{F}(r)}{\exp \left( {b - r} \right)}} \right){r}}}} & (4) \end{matrix}$

[0019] is set to 30 wt %·μm² or less.

[0020] The diffusion velocity of the above-mentioned mutual diffusion of Fe and Ge generated upon drawing results from the concentration gradient in the boundary portion between the region doped with F element and the region doped with GeO₂. The inventors have found that, when the radial distribution of doping amount of GeO₂ or F element in each region is set such that the weighted concentration gradients y_(G1), y_(F1), y_(G2), y_(F2) in boundary portions defined by equations (1) to (4) become predetermined values or less, the diffusion velocity of F and Ge lowers, thereby suppressing the mutual diffusion. As a consequence, desirable fiber characteristics are reliably obtained.

[0021] On the other hand, the method of making an optical fiber in accordance with the present invention comprises steps of: (1) preparing a silica glass pipe having a layer doped with GeO₂ at least on an inner periphery side thereof; (2) depositing undoped SiO₂ or SiO₂ doped with one or both of P and Cl onto the inside of the silica glass pipe, so as to produce a buffer layer; (3) inserting a silica glass rod doped with F element into the inside of the buffer layer, and then heating and unifying the silica glass rod and the buffer layer, so as to prepare an intermediate preform; and (4) melt-spinning an optical fiber preform including the intermediate preform. According to this method, an optical fiber having the above-mentioned buffer layer can be made favorably.

[0022] Alternatively, the method of making an optical fiber in accordance with the present invention comprises steps of: (1) preparing a silica glass pipe having a layer doped with GeO₂ at least on an inner periphery side thereof; (2) heating the silica glass pipe, so as to evaporate GeO₂ in its inner surface and eliminate at least a part thereof; (3) inserting a silica glass rod doped with F element into the inside of the silica glass pipe, and then heating and unifying the silica glass rod and the silica glass pipe, so as to prepare an intermediate preform; and (4) melt-spinning an optical fiber preform including the intermediate preform. According to this method, the above-mentioned optical fiber in which the germanium dioxide concentration in the vicinity of the boundary portion of the ring core region is lowered can be made favorably.

[0023] The method of making an optical fiber having an inner cladding region in accordance with the present invention includes the following three methods. The first method comprises steps of: (1) preparing a silica glass pipe having a layer doped with F at least on an inner periphery side thereof; (2) depositing undoped SiO₂ or SiO₂ doped with one or both of P and Cl onto the inside of the silica glass pipe, so as to form a buffer layer; (3) further forming at an inner peripheral portion thereof a glass layer doped with GeO₂, so as to produce an intermediate pipe; (4) inserting a silica glass rod into the inside of the intermediate pipe, and then heating and unifying the silica glass rod and the intermediate pipe, so as to prepare an intermediate preform; and (5) melt-spinning an optical fiber preform including the intermediate preform.

[0024] The second method comprises steps of: (1) concentrically forming, successively from the axial center side, a silica layer, a layer doped with GeO₂, and an undoped layer or a layer doped with one or both of P and Cl, so as to prepare a silica glass rod; (2) preparing a silica glass pipe having a layer doped with F element at least on an inner periphery side thereof; (3) inserting the silica glass rod into the silica glass pipe, and then heating and unifying the silica glass rod and the silica glass pipe, so as to prepare an intermediate preform; and (4) melt-spinning an optical fiber preform including the intermediate preform.

[0025] The third method comprises the steps of (1) and (2) steps of the first method; (3) forming a silica glass rod having a silica layer at the axial center and a layer doped with germanium dioxide therearound; (4) inserting the silica glass rod into the inside of the buffer layer, and then heating and unifying the silica glass rod and the buffer layer, so as to prepare an intermediate preform; and (5) melt-spinning an optical fiber preform including the intermediate preform. According to any of these methods, the optical fiber in accordance with the present invention having a buffer layer between the inner cladding region and the ring core region can be made favorably.

[0026] In the step of preparing the silica glass pipe in these methods, a silica glass rod having a layer doped with fluorine element or germanium dioxide at least on the inner periphery side thereof may be plastically deformed at a high temperature, so as to form an opening penetrating through the axial center, thereby yielding a glass pipe. Hence, a required silica glass pipe can be formed favorably.

[0027] Another method of making an optical fiber in accordance with the present invention comprises steps of: (1) preparing a silica glass rod having a silica layer on the axial center side and a ring-shaped layer doped with germanium dioxide disposed on the outside thereof; (2) opening the silica glass rod along the axis, so as to prepare a silica glass pipe; (3) inserting a silica glass rod doped with fluorine element into the inside of the silica glass pipe, and then heating and unifying the silica glass rod and the silica glass pipe, so as to form an intermediate preform; and (4) melt-spinning an optical fiber preform including the intermediate preform. The above-mentioned optical fiber having a buffer layer can favorably be made by this method as well.

[0028] The present invention will be more fully understood from the detailed description given hereinbelow and the accompanying drawings, which are given by way of illustration only and are not to be considered as limiting the present invention.

[0029] Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will be apparent to those skilled in the art from this detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

[0030]FIG. 1 is a lateral sectional view showing a structure of a first embodiment of the optical fiber in accordance with the present invention, whereas FIG. 2 is a chart showing the refractive index profile thereof;

[0031]FIG. 3 is a flowchart of a first method of making the optical fiber of FIG. 1, whereas FIGS. 4A to 4H are lateral sectional views showing the respective intermediate products at individual steps thereof;

[0032]FIG. 5 is a flowchart of a second method of making the optical fiber of FIG. 1, whereas FIGS. 6A to 6F are lateral sectional views showing the respective intermediate products at individual steps thereof;

[0033]FIG. 7 is a flowchart of a third method of making the optical fiber of FIG. 1, whereas FIGS. 8A to 8F are lateral sectional views showing the respective intermediate products at individual steps thereof;

[0034]FIGS. 9A to 9C are longitudinal sectional views showing respective steps of a method of making a silica glass tube;

[0035]FIG. 10 is a graph showing relationships between the thickness of an inner buffer layer and the transmission loss in optical fibers, whereas FIG. 11 is a graph showing relationships between the thickness of the inner buffer layer and the bending loss in optical fibers;

[0036]FIG. 12 is a graph showing relationships between the thickness of an outer buffer layer and the transmission loss in optical fibers, whereas FIG. 13 is a graph showing relationships between the thickness of the outer buffer layer and the bending loss in optical fibers;

[0037]FIG. 14 is a lateral sectional view showing a structure of a second embodiment of the optical fiber in accordance with the present invention, whereas FIG. 15 is a chart showing the refractive index profile thereof;

[0038]FIG. 16 is a flowchart of a method of making the optical fiber of FIG. 14, whereas FIGS. 17A to 17F are lateral sectional views showing the respective intermediate products at individual steps thereof;

[0039]FIG. 18 is a graph showing relationships between the GeO₂ concentration gradient y_(G1) in the inner boundary of a ring core region and the transmission loss in optical fibers;

[0040]FIG. 19 is a graph showing relationships between the GeO₂ concentration gradient y_(G2) in the outer boundary of the ring core region and the transmission loss in optical fibers;

[0041]FIG. 20 is a chart showing the refractive index profile of a third embodiment of the optical fiber in accordance with the present invention;

[0042]FIG. 21 is a graph showing relationships between the F element concentration gradient y_(F1) in the outer boundary of a center core region and the transmission loss in optical fibers;

[0043]FIG. 22 is a chart showing the refractive index profile of a fourth embodiment of the optical fiber in accordance with the present invention;

[0044]FIG. 23 is a graph showing relationships between the F element concentration gradient y_(F2) in the inner boundary of an inner cladding region and the transmission loss in optical fibers; and

[0045]FIGS. 24A and 24B are charts showing respective refractive index profiles of other embodiments of the optical fiber in accordance with the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] In the following, preferred embodiments of the present invention will be explained with reference to the accompanying drawings. To facilitate the comprehension of the explanation, the same reference numerals denote the same parts, where possible, throughout the drawings, and a repeated explanation will be omitted.

[0047]FIG. 1 is a view showing a cross-sectional structure of a first embodiment of the optical fiber in accordance with the present invention, whereas FIG. 2 shows the refractive index profile thereof.

[0048] The optical fiber in accordance with the first embodiment is made of silica glass, and is constituted, as shown in FIGS. 1 and 2, by a center core region 11 (having an outside diameter 2 a), an inner buffer layer 12 (having a thickness t₁), a ring core region 13 (having an outside diameter 2 b and a thickness t_(b)), an outer buffer layer 14 (having a thickness t₂), an inner cladding region 15 (having an outside diameter 2 c and a thickness t_(c)), and an outer cladding region 16, all of which are concentrically arranged successively from the center. Among them, both of the inner and outer buffer layers 12, 14 and the outer cladding region 16 are made of pure silica including substantially no additives except for P or Cl and have a refractive index n₀, the center core region 11 is doped with an adjusted amount of fluorine element so as to yield a refractive index n₁ which is lower than n₀, the ring core region 13 is doped with an adjusted amount of germanium dioxide so as to yield a refractive index n₂ which is higher than n₀, and the inner cladding region 15 is doped with fluorine element so as to yield a refractive index n₃ which is lower than n₀.

[0049] The outside diameter 2 a of the center core region 11 is a few micrometers, the outside diameter 2 b of the ring core region 13 is on the order of a few micrometers to 10 μm (the thickness t_(b) being about a few micrometers), the outside diameter 2 c of the inner cladding region 15 is a few micrometers to a few tens of micrometers (the thickness tc being on the order of a few micrometers to 10 μm, and the outside diameter of the outer cladding region 16 is normally 125 μm. Also, each of the respective thicknesses t₁, t₂ of the buffer layers 12, 14 is on the order of 0.01 to 5 μm. The relative refractive index difference Δn⁻=(n₁−n₀)/n₀ of the center core region 11 with reference to the refractive index n₀ of the outer cladding region 16 is −0.2% to −0.7%, and the relative refractive index difference Δn⁺=(n₂−n₀)/n₀ of the ring core region 13 with reference to the refractive index n₀ of the outer cladding region 16 is on the order of 0.5% to 1.5%.

[0050] Two kinds of different methods among methods of making this optical fiber will now be explained by way of example. FIG. 3 is a flowchart of a first method of making the optical fiber of FIG. 1, whereas FIGS. 4A to 4H are lateral sectional views showing the respective intermediate products at individual steps thereof.

[0051] First, at step S11, a starting glass tube 10 made of silica glass doped with F element is prepared (FIG. 4A). This starting glass tube 10 is to become an inner cladding region 15 having a low refractive index in the optical fiber, and has a tubular form with an inside diameter of 14 mm, an outside diameter of 25 mm, and a length of 300 mm, for example. Here, the concentration of doping F element is preferably on the order of 0.4 wt % to 1.5 wt %.

[0052] At step S12, undoped SiO₂ or SiO₂ doped with one or both of P and Cl is deposited with a thickness of about 0.06 mm on the inner peripheral face of the starting glass tube 10 by a CVD technique, so as to form the outer buffer layer 14 (FIG. 4B). Adding P or Cl to the outer buffer layer 14 adjusts the viscosity differences between this layer and the layers formed on both sides thereof, so that the drawing can stably be carried out when making the optical fiber. Subsequently, at step S13, SiO₂ doped with GeO₂ is deposited with a thickness of about 1.7 mm on the inner peripheral face of the outer buffer layer 14 by the CVD technique, so as to form the ring core region 13 (FIG. 4C). The concentration of GeO₂ added here is preferably on the order of 10 wt % to 30 wt %. As a consequence, the ring core region 13 attains a high refractive index. Further, at step S14, undoped SiO₂ or SiO₂ doped with one or both of P and Cl is deposited with a thickness of about 0.04 mm on the inner peripheral face of the ring core region 13 by the CVD technique, so as to form the inner buffer layer 12 (FIG. 4D). As a result, a multilayer glass tube 10 having an inside diameter of about 12.2 mm is obtained.

[0053] Adding P or Cl to silica glass forming the buffer layers 12, 14 can adjust the viscosity of each layer at the time of heating and melting, whereby the heating and drawing explained later can be carried out easily and reliably.

[0054] At step S15, a silica glass rod 11 a doped with F element, which is to become the center core region 11, is inserted into the inside of thus formed multilayer glass tube 10 (FIG. 4E). Here, the F element concentration in the center core region 11 is on the order of 0.5 wt % to 2.5 wt %. At this time, a gap may be formed between the multilayer glass tube 10 and the silica glass rod 11 a. However, for yielding an optical fiber whose core region has a low ellipticity, the gap is preferably as small as possible. Also, before the insertion, both or one of the multilayer glass tube 10 and the silica glass rod 11 a may be surface-treated with an HF solution or heated and extended until an appropriate diameter is attained. In the case where an oxygen/hydrogen flame is utilized for heating and extending the silica glass rod 11 a, the surface treatment with the HF solution is essential for eliminating the moisture attached to the surface of the silica glass rod 11 a.

[0055] At step S16, the multilayer glass tube 10 in the state where the silica glass rod 11 a is inserted therein is heated under a reduced pressure so as to unify them together, whereby a multilayer silica glass rod 20 is obtained (FIG. 4F). This heating and unifying step is carried out in an atmosphere of Cl₂ gas or a mixed gas made of Cl₂ gas and O₂ gas.

[0056] At step S17, this multilayer silica glass rod 20 is inserted into the inside of a pure silica glass tube 16 a (FIG. 4G). This pure silica glass tube 16 a is to become the outer cladding region 16 having a low refractive index in the optical fiber. Here, before the insertion, the multilayer silica glass rod 20 may be surface-treated with an HF solution or heated and extended until an appropriate diameter is attained. In the case where an oxygen/hydrogen flame is employed for heating and extending the multilayer silica glass rod 20, the surface treatment with the HF solution is essential for eliminating the moisture attached to the surface thereof.

[0057] Then, at step S18, the silica glass tube 16 a in the state where the multilayer silica glass rod 20 is inserted therein is heated under a reduced pressure so as to unify them together (FIG. 4H). As a result of the foregoing steps, an optical fiber preform is obtained. To extend a reduced length for optical fiber the optical fiber preform may be provided with an outer cladding by known VAD or OVD method. Thus manufactured optical fiber preform has a refractive index profile similar to that of the optical fiber shown in FIG. 2.

[0058] At step S19, this optical fiber preform is heated and drawn by a known technique, so as to yield an optical fiber having a desirable refractive index profile. When an optical fiber preform having such a refractive index profile is employed, the mutual diffusion of Ge atoms from the ring core region 13 to the center core region 11 and inner cladding region 15 caused by the diffusion of F atoms in the directions opposite thereto is prevented due to the existence of the buffer layers 12, 14 from occurring at the time of heating and drawing. Namely, the flowing of F atoms into the ring core region 13 and the flowing of Ge atoms from this region are suppressed, whereby the optical fiber can be prepared while the ring core region 13 is kept at a high refractive index state. Consequently, an optical fiber having favorable characteristics as a dispersion-shifted fiber can be obtained.

[0059] A second manufacturing method will now be explained with reference to FIGS. 5 and 6A to 6F. FIG. 5 is a flowchart showing this second manufacturing method, whereas FIGS. 6A to 6F are lateral sectional views showing the respective intermediate products at individual steps thereof.

[0060] First, at step S21, a silica glass tube 10 a doped with GeO₂ is prepared (FIG. 6A). This silica glass tube 10 a is to become the ring core region 13 having a high refractive index in the optical fiber, and has a tubular form with an inside diameter of about 15 mm, an outside diameter of about 24 mm, and a length of about 300 mm, for example. Its GeO₂ concentration is preferably 10 wt % to 30 wt %.

[0061] At step S22, undoped SiO₂ or SiO₂ doped with one or both of P and Cl is deposited with a thickness of about 0.3 mm on the inner peripheral face of the starting silica glass tube 10 a by a CVD technique, so as to form the inner buffer layer 12 (FIG. 6B).

[0062] At step S23, a silica glass rod 11 a doped with F element, which is to become the center core region 11, is inserted into the inside of the silica glass tube 10 a in which the buffer layer 12 (FIG. 6C) is formed. The F element concentration in the silica glass rod 11 a is 0.5 wt % to 2.5 wt %. At this time, a gap may be formed between the silica glass tube 10 a and the silica glass rod 11 a. However, for yielding an optical fiber whose core region has a low ellipticity, the gap is preferably as small as possible. Also, before the insertion, both or one of the silica glass tube 10 a and the silica glass rod 11 a may be surface-treated with an HF solution or heated and extended until an appropriate diameter is attained. In the case where an oxygen/hydrogen flame is utilized for heating and extending the silica glass rod 11 a, the surface treatment with the HF solution is essential for eliminating the moisture attached to the surface of the silica glass rod 11 a.

[0063] At step S24, the silica glass tube 10 a in the state where the silica glass rod 11 a is inserted therein is heated so as to unify them together (FIG. 6D). This heating and unifying step is carried out in an atmosphere of Cl₂ gas or a mixed gas made of Cl₂ gas and O₂ gas. Thus, a multilayer silica glass rod 20 a is obtained.

[0064] At step S25, the multilayer silica glass rod 20 a is inserted into the inside of a silica glass tube 21 having a region doped with F atoms on the inner periphery side and pure silica regions on both sides thereof (FIG. 6E). Here, the region doped with F atoms becomes the inner cladding region 15, the outer pure silica region becomes the outer cladding region 16, and the inner pure silica region becomes the outer buffer layer 14. Here, before the insertion, the multilayer silica glass rod 20 a may be surface-treated with an HF solution or heated and extended until an appropriate diameter is attained. In the case where an oxygen/hydrogen flame is employed for heating and extending the multilayer silica glass rod 20 a, the surface treatment with the HF solution is essential for eliminating the moisture attached to the surface thereof.

[0065] At step S26, the multilayer silica glass tube 21 in the state where the multilayer silica glass rod 20 a is inserted therein is heated so as to unify them together (FIG. 6F). As a result of the foregoing steps, an optical fiber preform is obtained. To extend a reduced length for optical fiber the optical fiber preform may be provided with an outer cladding by known VAD or OVD method. Thus manufactured optical fiber preform has a refractive index profile similar to that of the optical fiber shown in FIG. 2.

[0066] At step S27, the optical fiber preform thus obtained is heated and drawn by a known technique, so as to yield an optical fiber having a desirable refractive index profile. The optical fiber preform obtained at step S26 has a structure similar to that of the optical fiber obtained at step S18 in the first manufacturing method whose flowchart is shown in FIG. 3, whereby effects similar to those in the first manufacturing method are obtained in the second manufacturing method as well. Namely, an optical fiber having favorable characteristics as a dispersion-shifted optical fiber is obtained.

[0067] A third manufacturing method will now be explained with reference to FIGS. 7 and 8A to 8F. FIG. 7 is a flowchart showing this third manufacturing method, whereas FIGS. 8A to 8F are lateral sectional views showing the respective intermediate products at individual steps thereof.

[0068] First, at step S31, a multiplex silica glass tube 20 b is prepared (FIG. 8A). This multiplex silica glass tube 20 b is to become the ring core region 13 having a high refractive index in the optical fiber and the regions of buffer layers 12, 14 at its inner and outer peripheries; and is set such that its inside diameter is 14.4 mm, the inside and outside diameters of the ring core region 13 are 15 mm and 24 mm, respectively, and the outside diameter as a whole is, for example, 30 mm. Details of a method of making this multiplex silica glass tube will be explained later.

[0069] A silica glass rod 11 a doped with F element, which is to become the center core region 11, is inserted into the inside of the silica glass tube 20 b at step S32 (FIG. 8B), and they are heated in this inserted state so as to be unified together at step S33 (FIG. 8C). Since the details of these steps are identical to those of the above-mentioned steps S23, S24, they will not be explained here.

[0070] At step S34, the outer peripheral face of the unified silica glass rod 30 is eliminated by grinding or etching with an HF solution, so as to process the silica glass rod 30 such that its outside diameter becomes 1.1 times that of the ring core region 13 (FIG. 8D).

[0071] Thus processed silica glass rod 30 is inserted into the inside of a silica glass tube 21 having a region 15 doped with F atoms on the inner periphery side and pure silica region on outer side thereof at step S35 (FIG. 8E), and they are heated in this inserted state at step S36, so as to be unified (FIG. 8F). Since the details of these steps are identical to those of the above-mentioned steps S25, S26, they will not be explained here. As a result of the foregoing steps, an optical fiber preform is obtained. Thus manufactured optical fiber preform has a refractive index profile similar to that of the optical fiber shown in FIG. 2.

[0072] At step S37, the optical fiber preform thus obtained is heated and drawn by a known technique, so as to yield an optical fiber having a desirable refractive index profile. The optical fiber preform obtained at step S36 has a structure similar to that of the optical fibers obtained by the first and second manufacturing methods whose flowcharts are shown in FIGS. 3 and 5, whereby effects similar to those in the first and second manufacturing methods are obtained in the third manufacturing method as well. Namely, an optical fiber having favorable characteristics as a dispersion-shifted optical fiber is obtained.

[0073] For making various silica glass tubes used in the individual manufacturing methods, various techniques can be employed. For example, after a soot body is deposited on the outer periphery of a silica glass rod so as to produce a multilayer glass rod, the inner glass rod may be eliminated by boring or the like, so as to make a glass tube. Also, after a glass rod is produced by a known VAD or OVD technique, the inner glass rod may be eliminated by boring or the like, so as to make a glass tube.

[0074] In addition, piercing may be utilized to manufacture a silica glass tube. This manufacturing method will now be explained with reference to FIGS. 9A to 9C. FIGS. 9A to 9C are longitudinal sectional views showing the respective intermediate products at individual steps of this manufacturing method. Though an example in which a two-layer glass tube is made will be explained here, it is also applicable to the making of a single-layer glass tube or a multilayer glass tube having three or more layers.

[0075] First, a known VAD technique, OVD technique, or the like is utilized so as to make a glass rod 22′ having a region 22 a in the vicinity of the axial center and an outer peripheral region 22 b surrounding it (FIG. 9A). Then, this glass rod 22′ is heated in an inactive gas atmosphere to a temperature not lower than 1500° C. which is the softening temperature slightly lower than the melting point; and a rod 30 made of a heat-resistant material, such as tungsten, alumina, or carbon, for example, is inserted therein along the center axis as shown in FIG. 9B, so as to plastically deform the glass rod 22′, thus forming an opening along the center axis (piercing), whereby a silica glass tube 22 shown in FIG. 9C is obtained.

[0076] Thereafter, the surface of this silica glass pipe is dissolved with an HF solution having a concentration of 5% to 50%; or the silica glass pipe is heated to 1000° C. or higher, and processed by vapor-phase etching with SF₆ gas or the like, so as to eliminate at least 10 μm of the inner peripheral face, thereby smoothing it. As a consequence, after the processing, a silica glass pipe 22 having an inner face roughness of 10 μm or less, in which the boundary position between the inner region 22 a and the outer region 22 b deviates little in the axial direction, is obtained. Here, an SiO₂-GeO₂ glass layer may be deposited on the inner peripheral face of a silica glass pipe by an MCVD technique, and then the rod 30 may be inserted into this pipe so as to enhance the opening.

[0077] The inventors carried out experiments in which optical fibers were produced with different buffer layer thicknesses, and influences of the buffer layer thickness were compared with each other. Their results will now be reported.

[0078] First, influences of the inner buffer layer thickness were studied. Optical fibers produced according to the above-mentioned first manufacturing method were used for this comparative experiment, and their basic configurations are shown in Table 1. TABLE 1 Type 1 Type 2 Type 3 Center core region diameter 2a 4.0 μm Ring core region thickness t_(b) 7.5 μm Inner cladding region 12.0 μm thickness t_(c) Inner buffer layer thickness t₁ 0.001 μm to 5 μm Outer buffer layer thickness t₂ 0.5 μm F conc. of center core region 0.5 wt % 1.5 wt % 2.5 wt % GeO₂ conc. of ring core region 18 wt % F conc. of inner cladding region 0.5 wt %

[0079]FIG. 10 summarizes the change in transmission loss in each type of the optical fibers with respect to the thickness of the inner buffer layer, in which the abscissa indicates the varied inner buffer layer thickness, whereas the ordinate indicates the transmission loss at a wavelength of 1.55 μm. As the inner buffer layer became thicker, the transmission loss was reduced. When the inner buffer layer thickness exceeded 1 μm, there was substantially no difference in transmission loss even when the F element concentration of center core region differed. Based on the transmission loss alone, the inner buffer layer was preferably as thick as possible, and it was found preferable to have a thickness of at least 0.01 μm.

[0080] Table 2 lists transmission characteristics of five optical fibers with different inner buffer thicknesses among those of type 2 at the wavelength of 1.55 μm, whereas FIG. 11 is a graph of changes in bending loss at the wavelength of 1.55 μm with respect to the buffer layer thickness when these optical fibers were bent at a diameter of 20 mm (called as 20φ bending loss). TABLE 2 Inner buffer layer 0.001 0.01 0.1 1 5 thickness (μm) ______ Dispersion (ps/km/nm) −3.4 −3.4 −3.5 −1.0 5 Dispersion slope 0.077 0.078 0.077 0.075 0.084 (ps/km/nm²) Aeff (μm²) 83 84 85 89 160 20φ bending loss 0.4 0.4 0.6 5.0 100 (dB/m)

[0081] It can be seen that the bending loss increases as the inner buffer layer becomes thicker. From this viewpoint, it is preferred that the thickness of the inner buffer layer be 5 μm or less. From the foregoing results, it has been found preferable for the inner buffer layer to have a thickness of 0.01 μm to 5 μm.

[0082] Next, influences of the outer buffer layer thickness were studied. Optical fibers produced according to the above-mentioned first manufacturing method were also used for this comparative experiment, and their basic configurations are shown in Table 3. TABLE 3 Type 4 Type 5 Type 6 Center core region diameter 2a 3.6 μm Ring core region thickness t_(b) 1.5 μm Inner cladding region thickness 2.8 μm t_(c) Inner buffer layer thickness t₁ 0.4 μm Outer buffer layer thickness t₂ 0.001 μm to 5 μm F conc. of center core region 1.5 wt % GeO₂ conc. of ring core region 17 wt % F conc. of inner cladding region 0.3 wt % 0.5 wt % 1.5 wt %

[0083]FIG. 12 summarizes the change in transmission loss in each type of the optical fibers with respect to the thickness of the outer buffer layer, in which the abscissa indicates the varied outer buffer layer thickness, whereas the ordinate indicates the transmission loss at a wavelength of 1.55 μm. As with the inner buffer layer, as the outer buffer layer became thicker, the transmission loss was reduced. When the outer buffer layer thickness exceeded 1 μm, there was substantially no difference in transmission loss even when the F element concentration of center core region differed. Based on the transmission loss alone, the outer buffer layer was preferably as thick as possible, and it was found preferable to have a thickness of at least 0.01 μm.

[0084] Table 4 lists transmission characteristics of five optical fibers with different outer buffer thicknesses among those of type 5 at the wavelength of 1.55 μm, whereas FIG. 13 is a graph of changes in bending loss at the wavelength of 1.55 μm with respect to the outer buffer layer thickness when these optical fibers were bent at a diameter of 20 mm. TABLE 4 Outer buffer layer 0.001 0.01 0.1 1 5 thickness (μm) Dispersion (ps/km/nm) −2.0 −1.9 −2.1 1.0 4.0 Dispersion slope 0.075 0.074 0.075 0.074 0.084 (ps/km/nm²) Aeff (μm²) 75 77 75 73 78 20φ bending loss 0.3 0.2 0.2 0.4 0.1 (dB/m)

[0085] In the case of the outer buffer layer, though the dispersion value increases as the buffer layer is made thicker, no deterioration in bending loss or the like is seen, unlike the above-mentioned case of the inner buffer layer. As a consequence, it has been found that the outer buffer layer can be made thicker if it is at least 0.01 μm.

[0086] A second embodiment of the optical fiber in accordance with the present invention will now be explained. FIG. 14 is a view showing a cross-sectional structure thereof, whereas FIG. 15 shows the refractive index profile thereof.

[0087] The optical fiber in accordance with the second embodiment is made of silica glass, and is constituted, as shown in FIGS. 14 and 15, by a center core region 11 (having an outside diameter 2 a), a ring core region 13 (having an outside diameter 2 b and a thickness t_(b)), an inner cladding region 15 (having an outside diameter 2 c and a thickness t_(c)), and an outer cladding region 16 which are concentrically arranged successively from the center. It differs from the first embodiment shown in FIGS. 1 and 2 in that it does not include the buffer layers 12, 14 existing in the first embodiment, and that the radial distribution of the refractive index in the ring core region is not uniform but attains a maximum value n₂ in a middle portion. This structure is realized by radially changing the GeO₂ concentration in the ring core region 13 such that the concentration is lower in the boundary portion between the center core region 11 and inner cladding region 15 and higher in the middle portion.

[0088] Here, the concentration of GeO₂ is preferably set such that, letting C_(G)(r) [wt %] be the concentration of GeO₂ in the ring core region 13 at a position separated from the center by the radius r [μm], the concentration gradient y_(G1) [wt %·μ²] of GeO₂ in the boundary portion of the ring core region 13 with respect to the center core region 11 defined by the above-mentioned equation (1): $\begin{matrix} {y_{G1} = {\int_{a}^{a + 1}{\left( {{{rC}_{G}(r)}{\exp \left( {a - r} \right)}} \right){r}}}} & (1) \end{matrix}$

[0089] is 100 wt %·μm² or less, and the concentration gradient y_(G2) [wt %·μm²] of GeO₂ in the boundary portion of the ring core region 13 with respect to the inner cladding region 15 defined by the above-mentioned equation (3): $\begin{matrix} {y_{G2} = {\int_{b - 1}^{b}{\left( {{{rC}_{G}(r)}{\exp \left( {r - b} \right)}} \right){r}}}} & (3) \end{matrix}$

[0090] is 180 wt %·μm² or less. Here, y_(G1)=0 and y_(G2)=0 means that there is a buffer region 1 micrometers in thickness respectively.

[0091] An example of the method of making this optical fiber will be explained in the following. FIG. 16 is a flowchart showing this manufacturing method, whereas FIGS. 17A to 17F are lateral sectional views showing the respective intermediate products at individual steps thereof.

[0092] First, at step S41, a starting glass tube 13 b made of GeO₂-doped silica glass is prepared (FIG. 17A). This starting glass tube 13 b becomes the ring core region 13. The GeO₂ concentration distribution is uniform within the glass tube 13 b, and the concentration is 10 wt % to 40 wt %.

[0093] Subsequently, at step S42, the starting glass tube 13 b is heated, so as to evaporate GeO₂ from the inner and outer peripheries thereof and eliminate GeO₂ from the regions in the vicinity of the inner and outer peripheries, thereby yielding the ring core region 13 having a refractive index profile such as that shown in FIG. 15 (FIG. 17B).

[0094] A silica glass rod 23 doped with F element, which is to become the center core region 11, is inserted into the inside of the starting glass tube 13 b at step S43 (FIG. 17C), and is heated at step S44 so as to unify them, thereby yielding a multilayer glass rod 24 (FIG. 17D).

[0095] Since the respective steps of S45 to S47 (FIGS. 17E and 17F) are similar to steps of S25 to S27 (FIGS. 6E and 6F) shown in FIG. 5, they will not be explained here. Hence, an optical fiber preform having the refractive index profile shown in FIG. 15 is yielded, and an optical fiber is obtained when this optical fiber preform is drawn.

[0096] In this embodiment, at the time of heating and drawing, the diffusion of Ge atoms from the ring core region 13 to the center core region 11 and inner cladding region 15 is restrained since their diffusion velocities are suppressed because of the fact that the concentration gradient of GeO₂ is set low in their boundary portions. Together therewith, the inflow of F atoms in the opposite directions is restrained. As a result, an optical fiber can be made while the ring core region 13 is kept at a high refractive index state. Consequently, an optical fiber having favorable characteristics as a dispersion-shifted fiber can be obtained.

[0097] As a matter of course, a known VAD technique or OVD technique may be used so as to radially change the doping GeO₂ concentration, thereby forming the ring core region 13. Further, glass may be deposited while varying its GeO₂ concentration onto the inner and outer peripheral faces of a glass tube having a uniform doped GeO₂ concentration, so as to form a concentration gradient region. Alternatively, a known MCVD technique may be used such that the doping GeO₂ concentration at the time when depositing a synthetic glass layer on the inner face of a pure silica or fluorine-doped silica glass pipe successively becomes lower, higher, and lower, so as to form a concentration gradient region.

[0098] The inventors carried out experiments in which optical fibers were produced with different GeO₂ concentration gradients y_(G1), y_(G2) in the boundary portions on both sides of the ring core region 13, and influences of the concentration gradients were compared with each other. Their results will now be reported.

[0099] First, influences of the GeO₂ concentration gradient y_(G1) in the boundary portion between the ring core region 13 and the center core region 11 were studied. Optical fibers produced according to the above-mentioned manufacturing method were used for this comparative experiment. Their basic configurations are shown in Table 5. TABLE 5 Type 7 Type 8 Type 9 Center core region diameter 2a 5.0 μm Ring core region diameter 2b 8.3 μm Inner cladding region diameter 2c 14.0 μm concentration gradient y_(G1) 10 to 150 wt % · μm² F conc. of center core region 1.5 wt % GeO₂ peak conc. of ring core region 20 wt % 30 wt % 40 wt % F conc. of inner cladding region 0.5 wt %

[0100]FIG. 18 summarizes the results of the comparative experiment, in which the abscissa indicates the varied values of GeO₂ concentration gradient y_(G1) in the inner interface of the ring core region 13, whereas the ordinate indicates the transmission loss at the wavelength of 1.55 μm. Though no difference is seen in the case where the concentration gradient y_(G1) exceeds 100 wt %·μm², the transmission loss becomes smaller as the concentration gradient y_(G1) is made lower when it is not greater than 100 wt %·μm². From this point, it has been found preferable for the GeO₂ concentration gradient y_(G1) in the inner interface of the ring core region 13 to be 100 wt %·mμ² or less.

[0101] Next, influences of the GeO₂ concentration gradient y_(G2) in the boundary portion between the ring core region 13 and the inner cladding region 15 were studied. Optical fibers produced according to the above-mentioned manufacturing method were used for this comparative experiment as well. Their basic configurations are shown in Table 6. TABLE 6 Type 10 Type 11 Type 12 Center core region diameter 2a 4.5 μm Ring core region diameter 2b 8.0 μm Inner cladding region diameter 2c 13.0 μm concentration gradient y_(G2) 1 to 200 wt % · μm² F conc. of center core region 1.5 wt % GeO₂ peak conc. of ring core region 20 wt % 30 wt % 40 wt % F conc. of inner cladding region 1.0 wt %

[0102]FIG. 19 summarizes the results of the comparative experiment, in which the abscissa indicates the varied values of GeO₂ concentration gradient y_(G2) in the outer interface of the ring core region 13, whereas the ordinate indicates the transmission loss at the wavelength of 1.55 μm. As with the above-mentioned concentration gradient y_(G1), though no difference is seen in the case where the concentration gradient y_(G2) is at a predetermined value or greater, exceeding 180 wt %·μm² in this case, the transmission loss becomes smaller as the concentration gradient y_(G2) is made lower when it is not greater than 180 wt %·μm². From this point, it has been found preferable for the concentration gradient y_(G2) in the outer interface of the ring core region 13 to be 180 wt %·μm² or less.

[0103] Though the foregoing two embodiments are explained as embodiments in which both of the ring core region and center core region or both of the ring core region and inner cladding region are provided with buffer layers, or both of the ring core region and center core region or both of the ring core region and inner cladding region are provided with concentration gradient regions; one of them may be provided with a buffer layer, while the other is provided with a concentration gradient region.

[0104] A third embodiment of the optical fiber in accordance with the present invention will now be explained. The cross-sectional structure of this embodiment is similar to that in the second embodiment shown in FIG. 14 but differs therefrom in that it has the refractive index profile shown in FIG. 20. Namely, while the radial distribution of refractive index in the ring core region 13 is made uniform, the radial distribution of refractive index in the center core region 11 is not uniform but attains a minimum value n₁ in the center portion thereof. That is, a concentration gradient region exists only in the inside of the ring core region 13. This structure is realized by gradually decreasing the F concentration in the center core region 11 from the center portion to the boundary portion with respect to the ring core region 13. Preferably, this concentration distribution is set such that, letting C_(F)(r) [wt %] be the concentration of F element at a position in the center core region 11 separated from the center by the radius r [μm], the concentration gradient y_(F1) [wt %·μm²] of F in the boundary portion of the center core region 11 with respect to the ring core region 13 defined by the above-mentioned equation (2): $\begin{matrix} {y_{F1} = {\int_{a - 1}^{a}{\left( {{{rC}_{F}(r)}{\exp \left( {r - a} \right)}} \right){r}}}} & (2) \end{matrix}$

[0105] is 18 wt %·μm² or less. In the case of Y_(F1)=0, the thickness of inner buffer layer is 1 μm.

[0106] This optical fiber can be made by the steps of preparing, as a multilayer silica glass tube, the ring core region 13 and the regions outside thereof excluding the center core region 11; inserting a silica glass rod having a higher F-doping concentration in the center portion thereof into the inside of the glass tube; heating and unifying them together, so as to yield an optical fiber preform; and drawing this optical fiber preform.

[0107] The inventors carried out a comparative experiment in which optical fibers were produced with different F element concentration gradients y_(F1) in the outer boundary portion of the center core region 11, and influences of the concentration gradients y_(F1) were compared with each other. The results will now be reported.

[0108] Table 7 shows basic configurations of the optical fibers used for the comparative experiment. TABLE 7 Type 13 Type 14 Center core region diameter 2a 5.0 μm Ring core region diameter 2b 8.3 μm Inner cladding region diameter 2c 14 μm Concentration gradient y_(F1) 5 to 20 wt % · μm² F peak conc. of center core region 1.5 wt % 2.5 wt % GeO₂ conc. of ring core region 20 wt % F conc. of inner cladding region 0.5 wt %

[0109]FIG. 21 summarizes the results of the comparative experiment, in which the abscissa indicates the varied values of concentration gradient y_(F1), whereas the ordinate indicates the transmission loss at the wavelength of 1.55 μm. It was found that the transmission loss was reduced as the concentration gradient y_(F1) became lower, with its reducing effect being greater at 18 wt %·μm² or less. Therefore, the concentration gradient y_(F1) is preferably 18 wt %·m² or less.

[0110] A fourth embodiment of the optical fiber in accordance with the present invention will now be explained. The cross-sectional structure of this embodiment is similar to that in the second embodiment shown in FIG. 14 but differs therefrom in that it has the refractive index profile shown in FIG. 22. Namely, while the radial distribution of refractive index in the ring core region 13 is made uniform, the radial distribution of refractive index in the inner cladding region 15 is not uniform but attains a minimum value n₃ in the outer portion thereof. That is, a concentration gradient region exists only in the outside of the ring core region 13. This structure is realized by gradually increasing the F concentration in the inner cladding region 15 from the boundary portion with respect to the ring core region 13 to the outside. Preferably, this concentration distribution is set such that, letting C_(F)(r) [wt %] be the concentration of F element at a position in the inner cladding region 15 separated from the center by the radius r [μm], the concentration gradient y_(F2) [wt %·μm²] of F in the boundary portion of the inner cladding region 15 with respect to the ring core region 13 defined by the above-mentioned equation (4): $\begin{matrix} {y_{F2} = {\int_{b}^{b + 1}{\left( {{{rC}_{F}(r)}{\exp \left( {b - r} \right)}} \right){r}}}} & (4) \end{matrix}$

[0111] is 30 wt %·μm² or less. In the case of y_(F2)=0, the thickness of inner buffer layer is 1 μm.

[0112] This optical fiber can be made by the steps of preparing, as a multilayer silica glass rod, the ring core region 13 and region inside thereof; inserting it into a silica glass tube having an F-doped region on the inner side thereof with its concentration distribution becoming lower in the inner side; heating and unifying them together, so as to yield an optical fiber preform; and drawing this optical fiber preform.

[0113] The inventors carried out a comparative experiment in which optical fibers were produced with different F element concentration gradients y_(F2) in the inner boundary portion of the inner cladding region 15, and influences of the concentration gradients y_(F2) were compared with each other. The results will now be reported.

[0114] Table 8 shows basic configurations of the optical fibers used for the comparative experiment. TABLE 8 Type 15 Type 16 Center core region diameter 2a 4.6 μm Ring core region diameter 2b 8.0 μm Inner cladding region diameter 2c 14 μm F conc. of center core region 1.5 wt % GeO₂ conc. of ring core region 20 wt % concentration gradient y_(F2) 5 to 40 wt % · μm² F peak conc. of inner cladding region 1.5 wt % 2.5 wt %

[0115]FIG. 23 summarizes the results of the comparative experiment, in which the abscissa indicates the varied values of concentration gradient y_(F2), whereas the ordinate indicates the transmission loss at the wavelength of 1.55 μm. It was found that the transmission loss was reduced as the concentration gradient y_(F2) became lower, with its reducing effect being greater at 30 wt %·μm² or less. Therefore, the concentration gradient y_(F2) is preferably 30 wt %·μ² or less.

[0116] The buffer layers or concentration gradient regions formed on both sides of the ring core region can produce various types of optical fibers by combining the foregoing embodiments.

[0117] Further, the ring core region 13 is not restricted to a single one shown in FIG. 1, 14, 20, or 22, but a plurality of ring core regions 13 having a higher refractive index may be disposed in a multilayer form as shown in FIG. 24A or 24B. Preferably, in this case, buffer layers 12, 14 or concentration gradient regions are disposed between the individual GeO₂-doped higher refractive index regions 13 and F-doped low refractive index regions 11 in the ring core regions.

[0118] From the invention thus described, it will be obvious that the invention may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended for inclusion within the scope of the following claims. 

What is claimed is:
 1. An optical fiber, composed of silica glass, having a center core region doped with fluorine element and a ring core region doped with germanium dioxide; said optical fiber further comprising a buffer layer disposed between said center core region and said ring core region, said buffer layer being composed of undoped silicon dioxide or silicon dioxide doped with one or both of phosphorus and chlorine.
 2. An optical fiber according to claim 1, wherein said buffer layer has a thickness of at least 0.01 μm but not greater than 5 μm.
 3. An optical fiber, composed of silica glass, having a center core region doped with fluorine element and a ring core region doped with germanium dioxide; wherein, letting a [μm] be the radius of said center core region, and C_(G)(r) [wt %] be the concentration of germanium dioxide in said ring core region at a position separated from the center by a radius r [μm], the concentration gradient y_(G1) [wt %·μm²] of germanium dioxide in a boundary portion of said ring core region with respect to said center core region defined by: $\begin{matrix} {y_{G1} = {\int_{a}^{a + 1}{\left( {{{rC}_{G}(r)}{\exp \left( {a - r} \right)}} \right){r}}}} & (1) \end{matrix}$

is 100 wt %·μm² or less.
 4. An optical fiber, composed of silica glass, having a center core region doped with fluorine element and a ring core region doped with germanium dioxide; wherein, letting a [μm] be the radius of said center core region, and C_(F)(r) [wt %] be the concentration of fluorine element in said center core region at a position separated from the center by a radius r [μm], the concentration gradient y_(F1) [wt %·μm²] of fluorine element in a boundary portion of said center core region with respect to said ring core region defined by: $\begin{matrix} {y_{F1} = {\int_{a - 1}^{a}{\left( {{{rC}_{F}(r)}{\exp \left( {r - a} \right)}} \right){r}}}} & (2) \end{matrix}$

is 18 wt %·μm² or less.
 5. An optical fiber, composed of silica glass, having a center core region, a ring core region doped with germanium dioxide, and an inner cladding region doped with fluorine element, all of which are arranged concentrically; said optical fiber further comprising a buffer layer disposed between said ring core region and said inner cladding region, said buffer layer being composed of undoped silicon dioxide or silicon dioxide doped with one or both of phosphorus and chlorine.
 6. An optical fiber according to claim 5, wherein said buffer layer has a thickness of at least 0.01 μm.
 7. An optical fiber, composed of silica glass, having a center core region, a ring core region doped with germanium dioxide, and an inner cladding region doped with fluorine element; wherein, letting b [μm] be the radius of said ring core region, and C_(G)(r) [wt %] be the concentration of germanium dioxide in said ring core region at a position separated from the center by a radius r [μm], the concentration gradient y_(G2) [wt %·μm²] of germanium dioxide in a boundary portion of said ring core region with respect to said inner cladding region defined by: $\begin{matrix} {y_{G2} = {\int_{b - 1}^{b}{\left( {{{rC}_{G}(r)}{\exp \left( {r - b} \right)}} \right){r}}}} & (3) \end{matrix}$

is 180 wt %·μm² or less.
 8. An optical fiber, composed of silica glass, having a center core region, a ring core region doped with germanium dioxide, and an inner cladding region doped with fluorine element, all of which are arranged concentrically; wherein, letting b [μm] be the radius of said ring core region, and C_(F)(r) [wt %] be the concentration of fluorine element in said inner cladding region at a position separated from the center by a radius r [μm], the concentration gradient y_(F2) [wt %·μm²] of fluorine element in a boundary portion of said inner cladding region with respect to said ring core region defined by: $\begin{matrix} {y_{F2} = {\int_{b}^{b + 1}{\left( {{{rC}_{F}(r)}{\exp \left( {b - r} \right)}} \right){r}}}} & (4) \end{matrix}$

is 30 wt %·μm² or less.
 9. A method of making an optical fiber comprising the steps of: preparing a silica glass pipe having a layer doped with germanium dioxide at least on an inner periphery side thereof; depositing undoped silicon dioxide or silicon dioxide doped with one or both of phosphorus and chlorine onto the inside of said silica glass pipe, so as to produce a buffer layer; inserting a silica glass rod doped with fluorine element into the inside of said buffer layer, and then heating and unifying said silica glass rod and said buffer layer, so as to prepare an intermediate preform; and melt-spinning an optical fiber preform including said intermediate preform.
 10. A method of making an optical fiber according to claim 9, wherein, in the step of preparing said silica glass pipe, a silica glass rod having a layer doped with germanium dioxide at least on an inner periphery side thereof is plastically deformed at a high temperature, so as to form an opening penetrating through the axial center, thereby yielding a glass pipe.
 11. A method of making an optical fiber comprising the steps of: preparing a silica glass pipe having a layer doped with germanium dioxide at least on an inner periphery side thereof; heating said silica glass pipe, so as to evaporate germanium dioxide in an inner surface thereof and eliminate germanium dioxide in a surface layer; inserting a silica glass rod doped with fluorine element into the inside of said silica glass pipe, and then heating and unifying said silica glass rod and said silica glass pipe, so as to prepare an intermediate preform; and melt-spinning an optical fiber preform including said intermediate preform.
 12. A method of making an optical fiber according to claim 11, wherein, in the step of preparing said silica glass pipe, a silica glass rod having a layer doped with germanium dioxide at least on an inner periphery side thereof is plastically deformed at a high temperature, so as to form an opening penetrating through the axial center, thereby yielding a glass pipe.
 13. A method of making an optical fiber comprising the steps of: preparing a silica glass pipe having a layer doped with fluorine at least on an inner periphery side thereof; depositing undoped silicon dioxide or silicon dioxide doped with one or both of phosphorus and chlorine onto the inside of said silica glass pipe, so as to form a buffer layer; further forming at an inner peripheral portion thereof a glass layer doped with germanium dioxide, so as to produce an intermediate pipe; inserting a silica glass rod into the inside of said intermediate pipe, and then heating and unifying said silica glass rod and said intermediate pipe, so as to prepare an intermediate preform; and melt-spinning an optical-fiber preform including said intermediate preform.
 14. A method of making an optical fiber according to claim 13, wherein, in the step of preparing said silica glass pipe, a silica glass rod having a layer doped with fluorine at least on an inner periphery side thereof is plastically deformed at a high temperature, so as to form an opening penetrating through the axial center, thereby yielding a glass pipe.
 15. A method of making an optical fiber comprising the steps of: concentrically forming, successively from the axial center side, a silica layer, a layer doped with germanium dioxide, and an undoped layer or a layer doped with one or both of phosphorus and chlorine, so as to prepare a silica glass rod; preparing a silica glass pipe having a layer doped with fluorine at least on an inner periphery side thereof; inserting said silica glass rod into said silica glass pipe, and then heating and unifying said silica glass rod and said silica glass pipe, so as to prepare an intermediate preform; and melt-spinning an optical fiber preform including said intermediate preform.
 16. A method of making an optical fiber according to claim 15, wherein, in the step of preparing said silica glass pipe, a silica glass rod having a layer doped with fluorine at least on an inner periphery side thereof is plastically deformed at a high temperature, so as to form an opening penetrating through the axial center, thereby yielding a glass pipe.
 17. A method of making an optical fiber comprising the steps of: preparing a silica glass pipe having a layer doped with fluorine at least on an inner periphery side thereof; depositing undoped silicon dioxide or silicon dioxide doped with one or both of phosphorus and chlorine onto the inside of said silica glass pipe, so as to form a buffer layer; forming a silica glass rod having a silica layer at the axial center and a layer doped with germanium dioxide therearound; inserting said silica glass rod into the inside of said buffer layer, and then heating and unifying said silica glass rod and said buffer layer, so as to prepare an intermediate preform; and melt-spinning an optical fiber preform including said intermediate preform.
 18. A method of making an optical fiber according to claim 17, wherein, in the step of preparing said silica glass pipe, a silica glass rod having a layer doped with fluorine at least on an inner periphery side thereof is plastically deformed at a high temperature, so as to form an opening penetrating through the axial center, thereby yielding a glass pipe.
 19. A method of making an optical fiber comprising the steps of: preparing a silica glass rod having a silica layer on the axial center side and a ring-shaped layer doped with germanium dioxide disposed on the outside thereof; opening said silica glass rod along the axis, so as to prepare a silica glass pipe; inserting a silica glass rod doped with fluorine element into the inside of said silica glass pipe, and then heating and unifying said silica glass rod and said silica glass pipe, so as to form an intermediate preform; and melt-spinning an optical fiber preform including said intermediate preform. 